CN112542327A - Hierarchical porous carbon cloth material, preparation method thereof and application of hierarchical porous carbon cloth material as supercapacitor electrode - Google Patents
Hierarchical porous carbon cloth material, preparation method thereof and application of hierarchical porous carbon cloth material as supercapacitor electrode Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 146
- 239000004744 fabric Substances 0.000 title claims abstract description 146
- 239000000463 material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title abstract description 19
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002073 nanorod Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 9
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000002149 hierarchical pore Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 abstract description 13
- 239000003792 electrolyte Substances 0.000 abstract description 13
- 239000003990 capacitor Substances 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000001354 calcination Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000002135 nanosheet Substances 0.000 abstract 2
- 238000002791 soaking Methods 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- 238000002484 cyclic voltammetry Methods 0.000 description 12
- 238000004146 energy storage Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 238000010277 constant-current charging Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y40/00—Manufacture or treatment of nanostructures
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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Abstract
The invention relates to the technical field of novel electrode materials, and particularly provides a preparation method of a hierarchical porous carbon cloth material and application of the hierarchical porous carbon cloth material as a super capacitor electrode, wherein the preparation method of the hierarchical porous carbon cloth material comprises the following steps: soaking the cleaned carbon cloth into a mixed solution of hexamethylenetetramine, zinc nitrate hexahydrate and ammonia water, stirring, transferring to a reaction kettle for hydrothermal reaction, growing ZnO nanosheets on the surface of the carbon cloth, cleaning the carbon cloth on which the ZnO nanosheets grow, and drying; and calcining the carbon cloth coated with the ZnO nanorods on the surface in the nitrogen atmosphere, cooling to room temperature, and cleaning with 3M HCl solution to obtain the graded porous carbon cloth. The surface of the hierarchical porous carbon cloth prepared by the method has a large number of interconnected pore channel structures, and when the hierarchical porous carbon cloth is used as a super capacitor electrode, the contact area of the electrode and electrolyte can be effectively increased, and the ion diffusion rate of the electrode during working is improved, so that the electrochemical performance of the electrode material is improved.
Description
Technical Field
The invention relates to the technical field of novel electrode materials, can be applied to the field of super capacitor electrodes, and particularly relates to a hierarchical porous carbon cloth material, a preparation method thereof and application of the hierarchical porous carbon cloth material as a super capacitor electrode.
Background
With the increasing consumption of fossil energy and the serious environmental pollution, the development and utilization of clean energy has become the focus of research in the energy field. However, clean energy sources such as solar energy and wind energy are often intermittent and uncertain and strongly depend on the natural environment, so that the development of an energy storage and conversion device matched with the clean energy sources is particularly urgent. Among the numerous energy storage devices, supercapacitors have attracted a lot of attention and have been rapidly developed at their high power density, fast charge-discharge characteristics and good cycle life. The electrode material has great influence on the energy storage performance of the super capacitor, the carbon material is the electrode material which is most mature in technology at the earliest research, but the pure carbon material has low specific surface area and relatively few active sites, and the energy density of the pure carbon material cannot meet the requirement of rapid development of an energy market. Therefore, the carbon cloth material with the hierarchical porous structure is developed, the specific surface area of the carbon cloth material is increased, the effective contact between the carbon cloth material and electrolyte is increased, and the practical application of the material in the field of energy storage is greatly promoted.
Disclosure of Invention
The invention aims to provide a hierarchical porous carbon cloth material, a preparation method thereof and application of the hierarchical porous carbon cloth material as a super capacitor electrode.
The technical scheme of the invention is as follows: a hierarchical porous carbon cloth material is characterized in that ZnO nanorods grow on a carbon cloth substrate through a hydrothermal method; and carrying out heat treatment at high temperature, and forming a large number of hierarchical pore structures on the surface of the carbon cloth by utilizing the reaction of ZnO and the carbon cloth at high temperature to obtain the hierarchical porous carbon cloth material.
The preparation method of the hierarchical porous carbon cloth material comprises the following steps:
(1) adding hexamethylenetetramine, zinc nitrate hexahydrate and ammonia water into deionized water, and fully stirring to obtain a mixed solution;
(2) placing carbon cloth in the solution obtained in the step (1) to perform hydrothermal reaction;
(3) and (3) annealing the ZnO nanorod coated carbon cloth material obtained in the step (2) in a nitrogen atmosphere, cooling to room temperature, and then cleaning for multiple times to obtain the hierarchical porous carbon cloth material.
In the preparation method of the hierarchical porous carbon cloth material, in the step (1), the proportion of the hexamethylenetetramine, the zinc nitrate hexahydrate, the ammonia water and the deionized water is 5 mmol: 5 mmol: 2mL of: 35 mL.
According to the preparation method of the hierarchical porous carbon cloth material, the hydrothermal reaction temperature in the step (2) is 95 ℃, and the reaction time is 24 hours.
In the method for preparing the hierarchical porous carbon cloth material, the annealing treatment of the carbon cloth material in the step (3) is to calcine the carbon cloth material for 2 hours at 600 ℃ in a nitrogen atmosphere, and then calcine the carbon cloth material for 2 hours at 950 ℃.
In the preparation method of the hierarchical porous carbon cloth material, in the step (3), the heating rate is 5 ℃/s.
According to the preparation method of the hierarchical porous carbon cloth material, the cleaning is carried out for multiple times by using 3M HCl solution, residual Zn and ZnO on the surface of the carbon cloth are removed, and the hierarchical pore structure on the surface of the carbon cloth is fully exposed.
The hierarchical porous carbon cloth material is applied as an electrode of a super capacitor.
The invention has the beneficial effects that: the hierarchical porous carbon cloth material provided by the invention has a large number of pore channel structures with different sizes, and can effectively shorten the mass transfer distance of ions in a material phase. The macroporous structure provides an ion storage space, and facilitates the electrolyte to be transmitted to the inside of the mesopores/micropores. The micropores and the mesopores can effectively increase the active surface area of the carbon cloth material and improve the energy storage utilization rate of the carbon cloth material.
Drawings
FIG. 1 is a low magnification SEM picture of a graded porous carbon cloth material prepared in example 1;
FIG. 2 is a high power SEM picture of a graded porous carbon cloth material prepared in example 1;
FIG. 3 is a cyclic voltammogram of the graded porous carbon cloth electrode substrate material of example 1 at a scan rate of 10 mV/s;
FIG. 4 is a charge-discharge curve of the graded porous carbon cloth electrode substrate material of example 1 at different current densities;
FIG. 5 is a cyclic voltammogram of the graded porous carbon cloth electrode base material of example 2 at a scan rate of 10 mV/s;
FIG. 6 is a charge-discharge curve of the graded porous carbon cloth electrode substrate material of example 2 at different current densities;
FIG. 7 is a cyclic voltammogram of the graded porous carbon cloth electrode substrate material of example 3 at a scan rate of 10 mV/s;
FIG. 8 is a charge and discharge curve of the graded porous carbon cloth electrode substrate material of example 3 at different current densities;
FIG. 9 is a cyclic voltammogram of the graded porous carbon cloth electrode substrate material of example 4 at a scan rate of 10 mV/s;
fig. 10 is a charge and discharge curve of the graded porous carbon cloth electrode substrate material of example 4 at different current densities.
Detailed Description
Example 1 preparation and application of a hierarchical porous carbon cloth material (one) preparation method is as follows:
1) 5mmol of hexamethylenetetramine, 5mmol of zinc nitrate and 2mL of ammonia water are dissolved in 35mL of deionized water, and the mixture is fully stirred to form a milky suspension. Then, the solution and the size are 3 multiplied by 3cm2The carbon cloth (washed by ethanol and deionized water for multiple times before use) is transferred into a reaction kettle to carry out hydrothermal reaction so that the surface of the carbon cloth is coated with a layer of ZnO nano-rods, the reaction temperature is 95 ℃, the reaction time is 24 hours, the surface of the carbon cloth is washed by deionized water for multiple times after the reaction, and the carbon cloth is dried at the temperature of 60 ℃.
2) Transferring the carbon cloth wrapped with the ZnO nano-rods into a tubular furnace, wherein the heating rate is 5 ℃/s, and N is2And (3) annealing treatment is carried out under protection, firstly, the carbon cloth is calcined at 600 ℃ for 2h, then, the temperature is raised to 950 ℃ for calcining for 2h, then, the annealed carbon cloth material is washed for many times by using 3M HCl solution and deionized water, the residual Zn and ZnO on the surface of the carbon cloth are removed, and the hierarchical pore structure on the surface of the carbon cloth is fully exposed. And drying to obtain the graded porous carbon cloth electrode substrate material for the supercapacitor.
(II) detection results:
fig. 1 is a low-magnification SEM picture of the hierarchical porous carbon cloth material prepared in example 1, and it can be seen from fig. 1 that the surface of the carbon cloth becomes rough and a uniform pore structure appears on the surface of the carbon fiber. Fig. 2 is a high-power SEM picture of the hierarchical porous carbon cloth material prepared in example 1, and it can be seen from fig. 2 that pore structures with different pore diameters are formed on the surface of the carbon fiber of the carbon cloth, and the pore channels and the large specific surface area are favorable for the sufficient contact with the electrolyte, so as to improve the diffusion rate of electrolyte ions, thereby improving the energy storage performance.
(III) electrochemical analysis results:
the method comprises the following steps: under normal temperature and normal pressure, a hierarchical porous carbon cloth material is used as a working electrode, a graphite foil is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, 5M NaCl is used as electrolyte, and a cyclic volt-ampere scanning test and a constant current charging and discharging test are carried out on the hierarchical porous carbon cloth electrode within a potential range of-0.5-0.5V (vs. SCE), so that the specific capacitance and the energy storage multiplying power performance of the hierarchical porous carbon cloth electrode are researched. FIG. 3 is a cyclic voltammogram of the graded porous carbon cloth electrode of example 1 at a scanning speed of 10mV/s, which shows that in a 5M NaCl electrolyte, the scanning speed is 10mV/s-1In the process, the graded porous electrode material shows a cyclic voltammetry curve which is approximate to a rectangle, and shows good double-layer capacitance behavior, and meanwhile, compared with pure carbon cloth, the specific capacitance of the graded porous electrode material is also greatly improved. FIG. 4 is a constant current charge and discharge curve of the graded porous carbon cloth electrode of example 1, which shows that when the current density is 2mA cm-2The specific capacitance of the area can reach 822mF cm-2When the current density is from 2mA cm-2Increased to 20mA cm-2When the specific capacitance is 68.1% of the initial specific capacitance, the better effect is shownThe rate capability of (2).
Example 2 preparation and application of hierarchical porous carbon cloth material
The preparation method comprises the following steps:
1) 5mmol of hexamethylenetetramine, 5mmol of zinc nitrate and 2mL of ammonia water are dissolved in 35mL of deionized water, and the mixture is fully stirred to form a milky suspension. Then, the solution and the size are 3 multiplied by 3cm2The carbon cloth (washed by ethanol and deionized water for multiple times before use) is transferred into a reaction kettle to carry out hydrothermal reaction so that the surface of the carbon cloth is coated with a layer of ZnO nano-rods, the reaction temperature is 95 ℃, the reaction time is 12 hours, the surface of the carbon cloth is washed by deionized water for multiple times after reaction, and the carbon cloth is dried at the temperature of 60 ℃.
2) Transferring the carbon cloth wrapped with the ZnO nano-rods into a tubular furnace, wherein the heating rate is 5 ℃/s, and N is2And (3) annealing treatment is carried out under protection, firstly, the carbon cloth is calcined at 600 ℃ for 2h, then, the temperature is raised to 950 ℃ for calcining for 2h, then, the annealed carbon cloth material is washed for many times by using 3M HCl solution and deionized water, the residual Zn and ZnO on the surface of the carbon cloth are removed, and the hierarchical pore structure on the surface of the carbon cloth is fully exposed. And drying to obtain the graded porous carbon cloth electrode substrate material for the supercapacitor.
(II) electrochemical analysis results:
the method comprises the following steps: under normal temperature and normal pressure, a hierarchical porous carbon cloth material is used as a working electrode, a graphite foil is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, 5M NaCl is used as electrolyte, and a cyclic volt-ampere scanning test and a constant current charging and discharging test are carried out on the hierarchical porous carbon cloth electrode within a potential range of-0.5-0.5V (vs. SCE), so that the specific capacitance and the energy storage multiplying power performance of the hierarchical porous carbon cloth electrode are researched. FIG. 5 is a cyclic voltammogram of the graded porous carbon cloth electrode of example 2 at a scanning speed of 10mV/s, which shows that in a 5M NaCl electrolyte, the scanning speed is 10mV/s-1In the process, the graded porous electrode material shows a cyclic voltammetry curve which is approximate to a rectangle, and shows good double-layer capacitance behavior, and meanwhile, compared with pure carbon cloth, the specific capacitance of the graded porous electrode material is also greatly improved. FIG. 6 is a constant current charge and discharge curve of the graded porous carbon cloth electrode of example 2, which shows that when the current density is 2mA cm-2The specific capacitance of the area can reach up to 462mF cm-2When the current density is from 2mA cm-2Increased to 20mA cm-2When the specific capacitance is 70.1% of the initial specific capacitance, the better rate performance is shown.
Example 3 preparation and application of hierarchical porous carbon cloth material
The preparation method comprises the following steps:
1) 5mmol of hexamethylenetetramine, 5mmol of zinc nitrate and 2mL of ammonia water are dissolved in 35mL of deionized water, and the mixture is fully stirred to form a milky suspension. Then, the solution and the size are 3 multiplied by 3cm2The carbon cloth (washed by ethanol and deionized water for multiple times before use) is transferred into a reaction kettle to carry out hydrothermal reaction so that the surface of the carbon cloth is coated with a layer of ZnO nano-rods, the reaction temperature is 95 ℃, the reaction time is 24 hours, the surface of the carbon cloth is washed by deionized water for multiple times after the reaction, and the carbon cloth is dried at the temperature of 60 ℃.
2) Transferring the carbon cloth wrapped with the ZnO nano-rods into a tubular furnace, wherein the heating rate is 5 ℃/s, and N is2And (3) annealing treatment is carried out under protection, firstly, the carbon cloth is calcined at 600 ℃ for 1h, then, the temperature is raised to 950 ℃ for calcining for 2h, then, the annealed carbon cloth material is repeatedly cleaned by using 3M HCl solution and deionized water, the residual Zn and ZnO on the surface of the carbon cloth are removed, and the hierarchical pore structure on the surface of the carbon cloth is fully exposed. And drying to obtain the graded porous carbon cloth electrode substrate material for the supercapacitor.
(II) electrochemical analysis results:
the method comprises the following steps: under normal temperature and normal pressure, a hierarchical porous carbon cloth material is used as a working electrode, a graphite foil is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, 5M NaCl is used as electrolyte, and a cyclic volt-ampere scanning test and a constant current charging and discharging test are carried out on the hierarchical porous carbon cloth electrode within a potential range of-0.5-0.5V (vs. SCE), so that the specific capacitance and the energy storage multiplying power performance of the hierarchical porous carbon cloth electrode are researched. FIG. 7 is a cyclic voltammogram of the graded porous carbon cloth electrode of example 3 at a scanning speed of 10mV/s, which shows that in a 5M NaCl electrolyte, the scanning speed is 10mV/s-1In the process, the graded porous electrode material shows a cyclic voltammetry curve which is approximate to a rectangle, and shows good double-layer capacitance behavior, and meanwhile, compared with pure carbon cloth, the specific capacitance of the graded porous electrode material is also greatly improved. FIG. 8 is a constant current charge and discharge curve of the graded porous carbon cloth electrode of example 3, which shows that the electrode can be charged when chargedThe current density was 2mA cm-2The specific capacitance of the area can reach up to 602mF cm-2When the current density is from 2mA cm-2Increased to 20mA cm-2When the specific capacitance is 58.4% of the initial specific capacitance.
Example 4 preparation and application of hierarchical porous carbon cloth material
The preparation method comprises the following steps:
1) 5mmol of hexamethylenetetramine, 3mmol of zinc nitrate and 2mL of ammonia water are dissolved in 35mL of deionized water, and the mixture is fully stirred to form a milky suspension. Then, the solution and the size are 3 multiplied by 3cm2The carbon cloth (washed by ethanol and deionized water for multiple times before use) is transferred into a reaction kettle to carry out hydrothermal reaction so that the surface of the carbon cloth is coated with a layer of ZnO nano-rods, the reaction temperature is 95 ℃, the reaction time is 24 hours, the surface of the carbon cloth is washed by deionized water for multiple times after the reaction, and the carbon cloth is dried at the temperature of 60 ℃.
2) Transferring the carbon cloth wrapped with the ZnO nano-rods into a tubular furnace, wherein the heating rate is 5 ℃/s, and N is2And (3) annealing treatment is carried out under protection, firstly, the carbon cloth is calcined at 600 ℃ for 2h, then, the temperature is raised to 950 ℃ for calcining for 2h, then, the annealed carbon cloth material is washed for many times by using 3M HCl solution and deionized water, the residual Zn and ZnO on the surface of the carbon cloth are removed, and the hierarchical pore structure on the surface of the carbon cloth is fully exposed. And drying to obtain the graded porous carbon cloth electrode substrate material for the supercapacitor.
(II) electrochemical analysis results:
the method comprises the following steps: under normal temperature and normal pressure, a hierarchical porous carbon cloth material is used as a working electrode, a graphite foil is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, 5M NaCl is used as electrolyte, and a cyclic volt-ampere scanning test and a constant current charging and discharging test are carried out on the hierarchical porous carbon cloth electrode within a potential range of-0.5-0.5V (vs. SCE), so that the specific capacitance and the energy storage multiplying power performance of the hierarchical porous carbon cloth electrode are researched. FIG. 9 is a cyclic voltammogram of the graded porous carbon cloth electrode of example 4 at a scanning speed of 10mV/s, which shows that in a 5M NaCl electrolyte, the scanning speed is 10mV/s-1In the process, the graded porous electrode material shows a cyclic voltammetry curve which is approximate to a rectangle, and shows good double-layer capacitance behavior, and meanwhile, compared with pure carbon cloth, the specific capacitance of the graded porous electrode material is also greatly improved. FIG. 10 shows an embodimentExample 4 constant current charge and discharge curve of graded porous carbon cloth electrode, as can be seen from the figure, when the current density is 2mA cm-2The specific capacitance of the area can reach 524mF cm-2When the current density is from 2mA cm-2Increased to 20mA cm-2When the specific capacitance is 62.4% of the initial specific capacitance, excellent rate performance is exhibited.
Claims (8)
1. A hierarchical porous carbon cloth material is characterized in that: growing ZnO nanorods on a carbon cloth substrate by a hydrothermal method; and carrying out heat treatment at high temperature, and forming a large number of hierarchical pore structures on the surface of the carbon cloth by utilizing the reaction of ZnO and the carbon cloth at high temperature to obtain the hierarchical porous carbon cloth material.
2. A method of preparing a hierarchical porous carbon cloth material as claimed in claim 1, comprising the steps of:
(1) adding hexamethylenetetramine, zinc nitrate hexahydrate and ammonia water into deionized water, and fully stirring to obtain a mixed solution;
(2) placing carbon cloth in the solution obtained in the step (1) to perform hydrothermal reaction;
(3) and (3) annealing the ZnO nanorod coated carbon cloth material obtained in the step (2) in a nitrogen atmosphere, cooling to room temperature, and then cleaning for multiple times to obtain the hierarchical porous carbon cloth material.
3. The method for preparing a hierarchical porous carbon cloth material according to claim 2, characterized in that: in the step (1), the proportion of the hexamethylenetetramine, the zinc nitrate hexahydrate, the ammonia water and the deionized water is 5 mmol: 5 mmol: 2mL of: 35 mL.
4. The method for preparing a hierarchical porous carbon cloth material according to claim 3, characterized in that: the hydrothermal reaction temperature in the step (2) is 95 ℃, and the reaction time is 24 h.
5. The method for preparing a hierarchical porous carbon cloth material according to claim 4, characterized in that: the annealing treatment of the carbon cloth material in the step (3) is to calcine the carbon cloth material for 2 hours at 600 ℃ in a nitrogen atmosphere and then calcine the carbon cloth material for 2 hours at 950 ℃.
6. The method for preparing a hierarchical porous carbon cloth material according to claim 5, characterized in that: in the step (3), the heating rate is 5 ℃/s.
7. The method for preparing a hierarchical porous carbon cloth material according to claim 6, characterized in that: the cleaning is to use 3M HCl solution to clean for a plurality of times to remove residual Zn and ZnO on the surface of the carbon cloth and fully expose the hierarchical pore structure on the surface of the carbon cloth.
8. Use of a hierarchical porous carbon cloth material according to claim 1 as an electrode for a supercapacitor.
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